Fluxed composites

ABSTRACT

A method and product which provides a solid, non-powdered homogeneous form to liquid and low melting point solid compounds which facilitates stability, storage, dispersability and handling and which may be added directly to formulations requiring the liquid compound or low melting point solid compound. The liquid or low melting point solid ingredient is combined with a binder which is comprised of at least a wax and thermoplastic polymer. During the method of forming the product, both the binder and the liquid compound (or low melting point solid compound) pass through a liquid phase during which they are mixed. The product is then formed and cooled.

The present application is a Divisional of U.S. Ser. No. 08/806,528,filed Feb. 24, 1997, now U.S. Pat. No. 6,214,913, which is a Divisionalapplication of U.S. Ser. No. 08/430,150, filed Apr. 26,1995 (now U.S.Pat. No. 5,621,032), which is a Divisional of U.S. Ser. No. 08/135,125,filed on Oct. 8,1993, now abandoned, which is a Continuation of U.S.Ser. No. 07/774,587, filed on Oct. 10, 1991, now abandoned.

BACKGROUND OF THE INVENTION

The large scale industrial and commercial uses of liquid and low meltingpoint solid bulk materials pose a multitude of practical problems. Suchmaterials are difficult to handle; their physical properties lead toinaccurate measurements. Their physical form frequently results in asignificant percentage of waste due to materials adhering to containersand handling equipment. Frequently, such materials have a limited shelflife due to decomposition. Decomposition presents a particular problemwith organic peroxides which, over time, become unstable and present anexplosive hazard. Low melting point solids, those solids having amelting point below 120° F., become semi-solid and usually tacky, asthey approach their melting point. While this may not present asignificant problem at room temperature, the ambient temperature in manyplant operations may exceed 100° F. and approach the melting point ofthe low melting point solids. Even if the ambient temperature is wellbelow the melting point of the low melting point solid, if the solid hasbeen previously exposed to temperatures near the melting point, theproduct may have partially melted and “coalesced” into a largeagglomerate.

Attempts have been made to address these problems by mixing certainliquid or low melting point solid materials with solid compounds therebygiving such materials an interim solid form so that they will remainsolid over a wider temperature range. The resulting product is thenadded to formulations which call for the liquid or low melting pointsolid. However, the products that result from such attempts havesignificant drawbacks. Frequently, the dispersion of the liquid or lowmelting solid material is not uniform; this results in a widevariability in the concentration of the material within the product.Variability is a particular problem in products which use mineralfillers, such as clay, as a binder component. Where the liquid or lowmelting point solid is absorbed or adsorbed onto a mineral filler likeclay, there is a strong tendency toward particle agglomeration,especially if the product experiences wide temperature variation duringtransportation and storage. Where a mineral such as clay is mixed into aliquid, the clay tends to settle out before the product fullysolidifies, resulting in a stratified product. This stratificationproduces an uneven concentration of the liquid or low melting pointsolid throughout the final product. Also, products that have a mineralfiller as a binder, present a dispersion problem during the productsincorporation into the end formulation, such as into a rubberformulation.

Also, such products frequently have a low “activity”, that is, theproduct contains a low percentage of the desired liquid or low meltingpoint solid ingredient. A higher activity is desired by the purchaserssince first, more of the desired liquid or low melting point solid isavailable for the money, and, second, since the product will havecorrespondingly less binder, there are fewer compatibility problemsbetween the binder and the purchaser's formulation which requires theliquid or low melting point solid.

In addition, such products are frequently powdered. Powders may presenta respiratory hazard for persons handling the product and may present anexplosive hazard as well. Furthermore, many products “bleed”, that is,the liquid ingredient tends to disassociate from the solid component.

It would be desirable to have a liquid or low melting point solid in asolid form, to facilitate handling, measuring and storing, and which canbe added directly to the processes which require the liquid or lowmelting point solid ingredient. It would also be desirable to have ahigh activity, homogenous product in a non-powdered form. Finally, aproduct that would fully melt into a formulation, such as a rubberformulation, during processing, eliminating the undispersed solidparticles, would be very desirable.

SUMMARY OF INVENTION

The present invention relates to either a liquid compound or a lowmelting point solid compound, referred to herein as “activeingredients”, uniformly mixed with a binder, to provide a solidcomposite of high activity and longer shelf life, and also relates tothe method of their preparation. The composites provide a temporary formfor liquid or low melting point solid ingredients; the composites may beincorporated into a variety of industrial and/or commercial processes inthe same way that the active ingredient would be used. The compositesmay be added to processes which tolerate the addition of the binder.Composites may be made of a variety of active ingredients, such as:organic dialkyl peroxides; modified melamine resins; cyanurates;aldehyde-amines; phenylamines; methacrylates; organo-silanes andorgano-phosphites. As used herein “composite” means a solid mixture ofan active ingredient and a binder. The “activity” of a particularcomposite, that is, the percentage of active ingredient in thecomposite, will depend upon the type of active ingredient. The activeingredient is “composited” by being combined with a thermoplasticbinder, which contains a wax, and a thermoplastic polymer. Dependingupon the type of active ingredient in the composite, the binder may alsocontain a compatibilizing agent such as a fatty acid or an ethylenevinyl acetate copolymer resin, or both. Optional minor components, suchas wetting agents, stabilizers, plasticizers, homogenizing agents andmineral oils may also be added.

The composite is prepared by blending the active ingredient with thebinder preferably while both are in a liquid phase, then cooling themixture and forming or shaping the composite, using conventional formingprocedures.

DETAILED DESCRIPTION OF THE INVENTION The Active Ingredient

According to the present invention, a variety of liquid and low meltingpoint solid active ingredients are “composited” to produce compositesthat are easier and safer to handle, easier to measure, have anincreased shelf life, and a high activity, that is, a high percentage,in some composites up to 80%, of the active ingredient. The maximumpercentage of active ingredient depends on the type of activeingredient. When more than the maximum percent of the active ingredientis present in the composite (and thus, less than minimum binder ispresent) the composite becomes oily, frosted and/or tacky. Thiscondition is often described as surface bloom. Where the activeingredient is present in the preferred amount, the composite has a highactivity without a surface bloom. Where the active ingredient is presentin an amount between the preferred amount and the maximum amount, thecomposite contains some surface bloom but may be satisfactory for someuses. While as little as about 1% active ingredient may be present inthe composite, the economic interests dictate that the composite have ahigher activity, usually at least 30%.

For organic peroxide, a high activity means the composite will haveabout 70% to about 80% organic peroxide. For cyanurates, modifiedmelamine resins, organo-silanes, organo-phosphites, and aldehyde-aminereaction products, a high activity means the composite will have about50% to about 80% active ingredient. For phenylamine based antidegradantsand methacrylates, a high activity means the composite will have about60% to about 80% active ingredient.

Composites may be made of a variety of organic peroxides, for example,dialkyl peroxides, including dicumyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,a,a′-di(t-butylperoxy)diisopropylbenzene,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 andbutyl-4,4-bis(t-butylperoxy) valerate. A suitable dicumyl peroxide issold by Hercules, Inc. under the tradename DICUP R, or by Akzo ChemicalsInc. under the tradename PERKADOX BC. A suitable2,5-dimethyl-2,5-di(t-butylperoxy)hexane is sold by Akzo Chemicals Inc.under the tradename TRIGONOX 101, or by Atochem under the tradenameLUPERSOL 101. A suitable a,a′-di(t-butyl peroxy)diisopropylbenzene issold by Hercules, Inc. under the tradename VULCUP R, or by Akzo underthe tradename PERKADOX 145. A suitable2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 is sold by Atochem under thetradename LUPERSOL 130 or by Akzo under the tradename TRIGONOX 145. Asuitable m-butyl-4,4-bis(t-butylperoxy) valerate is sold by Akzo underthe tradename TRIGONOX 17, or by Atochem under the tradename LUPEROX230.

The compositization of organic peroxides according to this inventionpreserves the shelf life of the peroxides, and thus is particularlybeneficial because peroxides are unstable and over time, present anexplosive hazard. In addition, many organic peroxides are semi-solids atoperating temperature and thus are difficult to handle and measurebecause of their tendency to stick to containers and to reagglomerate.The organic peroxide composites of the present invention overcome theseproblems.

A composite may be made containing a modified melamine resin, (alsoknown as modified melamine formaldehyde resin) such ashexamethoxymethylmelamine. A suitable hexamethoxymethylmelamine isavailable from American Cyanamid under the Trademark “Cyrez 963” or fromMonsanto Company under the Trademark “Resimene 3520”.Hexamethoxymethylmelamine is a methylene donor and is widely usedparticularly in the tire industry, as an adhesion promoter.

Composites may be made from cyanurates, such as triallyl cyanurate,which is a low melting point solid and triallyl isocyanurate, which is aliquid at room temperature. A suitable triallyl cyanurate is sold byAkzo under the tradename PERKALINK 300, or by American Cyanamid underthe tradename TRIALLYLCYANURATE. A suitable triallyl isocyanurate issold by Akzo under the tradename PERKALINK 301. Cyanurates are used invarious industrial applications as reactive monomers for free radicalpolymerization. In the rubber industry cyanurates are used as co-agents,in the non-sulfur, (peroxide) curing of rubber.

Composites may be made of phenylamine based antidegradants such as:phenylenediamines, such as N-phenyl-N′-2-octyl-p-phenylenediamine, whichis a liquid at room temperature; alkylated diphenylamines; and thereaction products of diphenylamines, such as the reaction product ofdiphenylamine and acetone, commercially available as “BLE-25” fromUniroyal. The BLE-25 formulation is proprietary; it is characterized bya viscosity of 25-50 poise at 86° F., and specific gravity of 1.08 to1.10. A suitable N-phenyl-N′-2-octyl-p-phenylenediamine is sold by UOPInc. under the tradename UOP 688. The phenylamine based antidegradantsserve as antidegradants in rubber compositions.

Composites may be made of methacrylates, such as trimethylolpropanetrimethacrylate and trimethylolpropane triacrylate. A suitabletrimethylolpropane trimethacrylate is sold by Sartomer Corporation underthe Trademark “Sartomer Resin 350”. A suitable trimethylolpropanetriacrylate is also sold by Sartomer Corporation under the Trademark“Sartomer Resin 351”. Methacrylates often serve as a co-agent in theperoxide curing of rubber.

Composites may be made of organo-silanes, such asbis(3-triethoxysilylpropyl)tetrasulfane and a liquid organo-functionalsilane known as “UCARSIL RC-1” and sold by Union Carbide. Theformulation of “UCARSIL RC-1” is proprietary. A suitablebis(3-triethoxysilylpropyl)tetrasulfane is sold by Degussa Corporationunder the tradename “SI-69”. Organo-silanes serve as adhesion promotersand coupling agents in rubber formulations.

A composite according to the present invention may also be made oforgano-phosphites, such as tri(monononylphenyl)phosphite andtri(dinonylphenyl)phosphite or mixtures thereof. A suitable mixture issold under the trademark “POLYGARD HR” by Uniroyal Chemical Company. Theorgano-phosphites serve as antidegradants in rubber compositions.

Composites may also be made of aldehyde-amine reaction products, such asbutyraldehyde-aniline reaction products, butyraldehyde-butylaminereaction products, formaldehyde-ammonia-ethyl chloride reactionproducts, and heptaldehyde-aniline reaction products. A suitablebutyraldehyde-butylamine reaction product is sold by R. T. Vanderbiltunder the tradename “VANAX 833”. A suitable formaldehyde-ammonia-ethylchloride reaction product is sold by Uniroyal under the tradename“TRIMENE BASE”. A suitable heptaldehyde-aniline reaction product is soldby Uniroyal under the tradename “HEPTEEN BASE”. Suitablebutyraldehyde-aniline reaction products are sold by R. T. Vanderbiltunder the tradenames “VANAX AT” and “Vanax 808”. The aldehyde-aminereaction products serve as accelerators in rubber formulations.

It should be understood that the active ingredients, particularlycommercial grades, depending on their source, may contain substantialamounts of a wide variety of impurities. Therefore, such impurities alsowill be incorporated into the composite.

The Binder

As used herein, the term “binder” includes all additives, except theactive ingredient, in the composite. The binder has a higher meltingpoint/softening point than the active ingredient, and imparts the solidform to the composite. The binder contains at least one wax, and atleast one thermoplastic polymer, for example, a polyolefin, preferablypolyethylene, most preferably oxidized polyethylene. Depending on thetype of active ingredient, the binder may also contain at least onecompatibilizing agent, for example, ethylene vinyl acetate copolymerresin or a fatty acid, or mixtures thereof. A compatibilizing agentpromotes the compatibility between the active ingredient and the binder,which promotes the cohesiveness of the composite. Where the activeingredient and the binder are of sufficiently different polarity so thatthe composite is not cohesive, a compatibilizing agent may be required.Optional minor components such as wetting agents, stabilizers,plasticizers, and mineral oils may also be added.

Any wax could be used, including, but not limited to, petroleum derivedwaxes such as paraffin and microcrystalline wax, and natural waxes suchas beeswax and carnauba. Good results have been obtained using paraffinwax or a microcrystalline wax or mixture of both. Paraffin is preferred.However, it should be understood that paraffin may contain somemicrocrystalline wax. While any paraffin wax may be used, good resultshave been obtained using a paraffin wax having a melting point in therange of 140° to 145° F. A suitable paraffin is sold by Astor WaxCompany available through M. F. Cachat, Cleveland, Ohio under theTrademark “Astax 140/145 Paraffin”. The wax helps impart the solid formto the binder.

A thermoplastic polymer, such as polyethylene, preferably oxidizedpolyethylene, promotes compatibility between the active ingredient andthe binder components and helps to impart the necessary hardness to thecomposite. A suitable oxidized polyethylene having a melting point fromabout 170° F. to about 250° F., a viscosity from about 80 to about 160cps at 120° C., and a hardness of from about 1 to about 5 penetrationunits at 25° C., is sold by Huls of Germany, and is available from M. F.Cachat, Cleveland, Ohio under the Trademark “Vestowax AO 1539”.

Depending on the active ingredient, a fatty acid may be added to thebinder. The addition of fatty acids improves the compatibility of theactive ingredient and the binder, and also lowers the initial meltingpoint of the composite. Preferably, fatty acid is added where the activeingredient is a modified melamine resin, a cyanurate, or a reactionproduct of acetone and diphenylamine. Due to the difficulty inseparating fatty acids, a fatty acid is a mixture of several differentfatty acids. Preferably, a fatty acid having a stearic acid content fromabout 10% to about 92% stearic acid, and more preferably, a high stearicacid content fatty acid having a stearic acid content of 70% is used.The other fatty acids present in the mixture typically include palmiticacid, oleic acid and myristic acid. These fatty acids may also be usedalone or in combination although they are not preferred. A suitable highstearic acid content fatty acid is sold by Witco Industries under theTrademark “HYSTRENE 7018”.

Depending on the type of active ingredient in the composite, an ethylenevinyl acetate copolymer resin may also be added. Preferably, ethylenevinyl acetate copolymer resin is added where the active ingredient is aphenylamine based antidegradant, a cyanurate, a modified melamine resin,an organo-phosphite, or the liquid organo-functional silane “RC-1”.Ethylene vinyl acetate copolymer resin acts as a homogenizer and alsoincreases the viscosity of the heated binder-active ingredient blend,which provides a more defined shape upon forming. Good results have beenobtained using an ethylene vinyl acetate copolymer resin having about18% vinyl acetate, about 82% ethylene and a softening point of 190° F. Asuitable resin is sold by DuPont DeNemours Company under the Tradename“Elvax” and also sold by Quantum Chemical under the Tradename“ULTRATHENE”.

The percentage of individual binder components will depend upon the typeof active ingredient in the composite. The following binder componentpercentages represent the percent of total binder composition. When theactive ingredient is an organic peroxide, the paraffin may be present inthe binder from about 20% to about 95%, preferably about 63.3%. Thepolyethylene is present in the binder from about 5% to about 80%,preferably about 36.7%.

Where the active ingredient is a modified melamine resin, such ashexamethoxymethylmelamine, the paraffin may be present in the binderfrom about 1% to 60% of the total binder composition, preferably about30%. The polyethylene is present in the binder from about 1% to about40%, preferably about 20%. In addition, the binder contains either fromabout 1% to about 40%, of ethylene vinyl acetate copolymer resin or fromabout 1% to about 50%, fatty acid, or both. Preferably, the bindercontains both fatty acid and ethylene vinyl acetate copolymer resin;preferably about 40% fatty acid and about 10% ethylene vinyl acetatecopolymer resin.

Where the active ingredient is a cyanurate, the paraffin is present into the binder in an amount from about 1% to about 60% of the totalbinder composition, preferably about 30%. The polyethylene is present inthe binder from about 1% to about 40%, preferably about 15%. Inaddition, the binder contains either from about 1% to about 40% ofethylene vinyl acetate copolymer resin or from about 1% to about 50%fatty acid, or both. Preferably, the binder contains both fatty acid andethylene vinyl acetate copolymer resin; preferably about 40% fatty acidand about 15% ethylene vinyl acetate copolymer resin.

Where the active ingredient is a phenylamine, such asN-phenyl-N′-2-octyl-p-phenylenediamine, the paraffin is present in thebinder in an amount from about 5% to about 70% of the total bindercomposition, preferably about 38%. The polyethylene is present in thebinder from about 1% to about 40 (preferably about 12%. Preferably fromabout 5% to about 70%, preferably about 50%, of ethylene vinyl acetatecopolymer resin is added.

Where the active ingredient is a liquid high temperature reactionproduct of acetone and a diphenylamine, such as “BLE-25”, the paraffinis present in the binder in an amount from about 5% to about 50% of thetotal binder composition, preferably about 20%. The polyethylene ispresent in the binder from about 1% to about 60%, preferably about 30%.In addition, the binder contains either from about 1% to about 60% ofethylene vinyl acetate copolymer resin or from about 1% to about 50%fatty acid, or both. Preferably, the binder contains both fatty acid andethylene vinyl acetate copolymer resin; preferably about 20% fatty acidand about 30% ethylene vinyl acetate copolymer resin.

Where the active ingredient is an organo-silane such asbis(3-triethoxysilylpropyl)tetrasulfane, the paraffin is present in thebinder in an amount from about 20% to about 95% of the total bindercomposition, preferably about 63.3%. The polyethylene is present in thebinder from about 5% to about 80%, preferably about 36.7%. Where theactive ingredient is the liquid organo-functional silane “UCARSIL RC-1”,the paraffin is present in the binder in an amount from about 5% toabout 70% of the total binder composition, preferably about 47.5%. Thepolyethylene is present in the binder from about 1% to about 50%,preferably about 27.5%. Preferably, ethylene vinyl acetate copolymerresin is also present in the binder from about 1% to about 60%, morepreferably about 25%.

Where the active ingredient is a methacrylate the paraffin is present inthe binder in an amount from about 20% to about 99% of the total bindercomposition, preferably about 63.3%. The oxidized polyethylene ispresent in the binder from about 1% to about 80%, preferably about36.7%.

Where the active ingredient is an organo-phosphite, the paraffin ispresent in the binder in an amount from about 5% to about 50% of thetotal binder composition, preferably about 20%. The oxidizedpolyethylene is present in the binder from about 1% to about 60%,preferably about 40%. Preferably, ethylene vinyl acetate copolymer resinis also present in the binder from about 1% to about 60%, morepreferably about 40%.

Where the active ingredient is an aldehyde-amine reaction product, theparaffin is present in the binder in an amount from about 5% to about95%, preferably about 50.6%. The oxidized polyethylene is present in thebinder from about 1% to about 60%, preferably about 29.4%. Preferably,ethylene vinyl acetate copolymer is also present in the binder fromabout 1% to about 50%, more preferably about 20%.

Additional components such as stabilizers, plasticizers, wetting agentsand mineral oils may be added, in minor amounts, to the binder.Stabilizers, such as hydroquinone, may be added to the binder in anamount from about 0.1% to about 10%, to prevent the oxidation orhydrolysis of the active ingredient in the composite. Plasticizers, suchas phthalate plasticizers, preferably diisodecylphthalate ordioctylphthalate may be added to the binder in an amount from about 1%to about 20% to decrease the melting point of the composite. Wettingagents, such as amine derivatives of fatty acids, may be added in anamount from 1% to about 50% to promote compatibility of the activeingredient in the composite. Mineral oils, such as paraffinic oils andnaphthenic oils, may be added to the binder to decrease the meltingpoint of the composite. A suitable paraffinic oil is sold by Sun Oilunder the Trademark “SunPar 2280”. A suitable naphthenic oil is sold byErgon under the Tradename “Hyprene V 2000”. The mineral oil is added inan amount sufficient to adjust the melting point of the composite to thedesired melting point.

The Composite

The composite of the active ingredient and the binder is prepared bycombining the active ingredient with the binder so that at some point inthe mixing procedure, the binder and the active ingredient are both in aliquid phase, and are then blended while both are in a liquid phase. Asused herein, “liquid phase” includes high viscosity paste-like phases.This may be accomplished by mixing the liquid active ingredient (or ifactive ingredient is a semi-solid, heating the active ingredient beyondits melting point) with a molten binder. Alternatively, the activeingredient may be mixed with a solid binder and the temperature of themixture raised above the melting points of the active ingredient and thebinder ingredients. Then, once both the active ingredient and binder arein a liquid phase, they are thoroughly blended to provide a homogenousmixture, at a temperature which will keep both the binder and activeingredient in a liquid phase. After a thorough blending, the homogenousmixture is cooled just above the melting point of the composite. Themixture is then fed through conventional forming processes so that thefinished composite may be in the form of pellets, pastilles, flakes,prills, powder or slabs, depending upon the desired form. A suitablemethod of forming the composites into pastilles, or half sphere shape,is by using a rotary head for forming drops onto a cooled stainlesssteel conveyor. This equipment is available from Sandvik Process SystemsInc.

It should be noted that as the percent of active ingredient in thecomposite is increased, (and the percentage of binder is correspondinglydecreased) the tolerances of the binder and its components becomenarrower. That is, as the percentage of active ingredient increases, thepercentage range of each binder component that will provide asatisfactory composite becomes narrower. Similarly, the type of thebinder components needed to provide a satisfactory composite also becomerestricted. Where the percentage of active ingredient is very high, thepreferred optional ingredients may become necessary ingredients; thatis, they become necessary to maintain the form of the composite. Whenthere is less binder in the composite, it becomes more difficult toobtain a solid composite and more difficult to form or shape thecomposite. These results affect not only the finished product, but alsoaffect the operating speed of the composite forming equipment and thestability of the composite during storage and transportation. Also,decreasing the binder percentage in the composite reduces thecompatibility between the active ingredient and the binder.

While the following examples of composites contain one activeingredient, more than one active ingredient may be added to a composite.It should be understood that composites having two or more activeingredients are within the scope of this invention.

The Organic Peroxide Composite

Organic peroxides, such as dialkyl peroxides may be present in thecomposite from about 30% to about 80%, preferably about 70%. The binderis present from about 20% to about 70%, preferably about 30%. Dialkylperoxide composites may be prepared as follows.

EXAMPLE 1

A dicumyl peroxide (DCP) composite was prepared by measuring 136kilograms of a recrystallized grade DCP, from Akzo Inc. which is 96-100%pure and has a melting point of about 100° F. The DCP was then placed ina vat with a hot water jacketing. The water temperature within thejacketing was controlled to yield a DCP temperature of from 150-160° F.The binder was prepared separately by melting together 36.7% of thetotal binder weight, or 21.4 kilograms of oxidized polyethylene(VESTOWAX AO 1539) having a melting point of 225° F. and 63.3%, or 36.9kilograms of ASTAX 140/145 paraffin. The polyethylene and paraffin werethoroughly blended together in a heated blend tank at 195° F. Then theDCP was added to the liquid binder. The DCP-binder mixture was thenthoroughly blended. (The addition of the DCP to the binder decreased thetemperature of the mixture roughly to 170° F.) When a homogenous mixturewas achieved, it was then fed in portions through a pelletizer, whilethe remainder was mildly agitated in the tank. The pelletizer, a Sandvikprocess system, dispensed the DCP-binder mixture in droplets onto a coldstainless steel conveyer belt. As a result, composite pellets in a“half-sphere” shape were produced.

EXAMPLE 1A

A dicumyl peroxide (DCP) composite was also prepared by first preparingthe binder. The binder was prepared by melting together 36.7% of thetotal binder weight, or 21.4 kilograms, of oxidized polyethylene(VESTOWAX AO 1539 having a melting point of 225° F. and 63.3%, or 36.9kilograms of ASTAX 140/145 paraffin. The polyethylene and paraffin werethoroughly blended together in a heated blend tank at 195° F. Then 136kilograms of a recrystallized grade DCP, from Akzo Chemical Inc. whichis 96-100% pure and has a melting point of about 100° F., was added tomolten binder. The DCP-binder mixture was then thoroughly blended. (Theaddition of the DCP to the binder decreases the temperature of themixture roughly to 170° F.) When a homogenous mixture was achieved, itwas then fed in portions through a pelletizer, while the remainder wasmildly agitated in the tank. The pelletizer, a Sandvik process system,dispensed the DCP-binder mixture in droplets onto a cold stainless steelconveyer belt. As a result, composite pellets in a “half-sphere” shapewere produced.

EXAMPLE 2

An a,a′di(t-butylperoxy)diisopropylbenzene composite was prepared byfirst preparing the binder which was made by placing 36.7% of the totalbinder weight, or 5.5 grams of oxidized polyethylene (VESTOWAX AO 1539)having a melting point of 225° F. and 63.3%, or 9.5 grams of ASTAX140/145 paraffin in an aluminum dish. The dish was then heated on a hotplate to melt the binder components. When temperature reached 250° F.and the binder components were completely melted, the binder wasthoroughly stirred. The binder was then cooled to just above 225° F. andthen 70% or 35 grams of a,a′di(t-butylperoxy)diisopropylbenzene wasadded. The a,a′di(t-butylperoxy)diisopropylbenzene-binder mixture wasmaintained at between 150-200° F. and thoroughly blended. When ahomogenous mixture was achieved, production methods for forming thecomposite were simulated by dispensing droplets from a stirring rod ontoa chilled metal surface, such as aluminum. As a result, compositepellets in a “half-sphere” shape were produced.

EXAMPLE 3

A 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (DBPH) composite was preparedas in Example 2. The binder was prepared by mixing together 36.7% of thetotal binder weight or 9.2 grams oxidized polyethylene, (VESTOWAX AO1539) and 63.3% or 15.8 grams of ASTAX 140/145 paraffin having a140-145° F. melting point. An equal weight, 25 grams, of DBPH, (LUPERSOL101) was added to the binder mixture while agitating the mixture. Thecomposite was prepared as in Example 2.

The Modified Melamine Resin Composite

The modified melamine resin, such as hexamethoxymethylmelamine, may bepresent in the composite in an amount of from about 1% to about 80%,preferably about 30% to about 70%, most preferably about 50%. The binderis present from about 20% to about 99%, preferably about 70% to about30%, most preferably about 50%. A hexamethoxymethylmelamine compositewas prepared as follows.

EXAMPLE 4

The composite was prepared as in Example 2. The binder was prepared bymixing together 20% of the total binder weight or 5 grams, oxidizedpolyethylene (VESTOWAX AO 1539), 30% or 7.5 grams, of ASTAX 140/145paraffin having a 140-145° F. melting point, 40% or 10 grams stearicacid (HYSTRENE 7018) and 10% or 2.5 grams EVA copolymer (ELVAX). Anequal weight, 25 grams of hexamethoxymethylmelamine, (CYREZ 963) wasadded to the binder mixture while agitating the mixture. The compositewas prepared as in Example 2.

The Cyanurate Composite

The cyanurate may be present in the composite in an amount from about 1%to about 80%, preferably 30% to about 70%, most preferably about 50%.The binder is present from about 20% to about 99%, preferably about 70%to about 30%, most preferably about 50%. A triallyl cyanurate (TAC)composite was prepared as follows.

EXAMPLE 5

The composite was prepared as in Example 2. The binder was prepared bymixing together 15% of the total binder weight or 3.75 grams of anethylene vinyl acetate copolymer resin, (ELVAX), 15% or 3.75 gramsoxidized polyethylene, (VESTOWAX AO 1539), 40% or 10 grams high stearicacid content fatty acid (HYSTERENE 7018) and 30% or 7.5 grams ASTAX140/145 paraffin having a 140-145° F. melting point. An equal weight, 25grams of TAC, (PERKALINK 300) was added to the binder mixture whileagitating the mixture. The composite was prepared as in Example 2.

The Phenylamine Composite

Phenylamines, particularly phenylamine based antidegradants, may bepresent in the composite in an amount from about 30% to about 80%,preferably about 60%. The binder is present from about 20% to about 70%,preferably about 30% to about 50%, preferably about 40%. Phenylaminecomposites may be prepared as follows.

EXAMPLE 6

A composite of N-phenyl-N′-2-octyl-p-phenylenediamine was prepared as inExample 2. The binder was prepared by mixing together 50% of the totalbinder weight or 10 grams of an ethylene vinyl acetate copolymer resin,(ELVAX) 12% or 2.4 grams oxidized polyethylene (VESTOWAX 1539) and 38%or 7.6 grams ASTAX 140/145paraffin having a 140-145° F. melting point.Then 30 grams of N-phenyl-N′-2-octyl-p-phenylenediamine, (UOP 688) wasadded to the binder mixture while agitating the mixture. The compositewas prepared as in Example 2.

EXAMPLE 7

A composite of a high temperature reaction product of acetone anddiphenylamine, commercially available as “BLE-25” from Uniroyal ChemicalCompany, was prepared as in Example 2. The binder was prepared by mixingtogether 30% of the total binder weight or 7.5 grams of an ethylenevinyl acetate copolymer resin, (ELVAX) 30% or 7.5 grams oxidizedpolyethylene, (VESTOWAX AO 1539) 20% or 5 grams ASTAX 140/145 paraffinhaving a 140-145° F. melting point, and 20% or 5 grams of a high stearicacid content fatty acid. An equal weight, 25 grams, of BLE-25 was addedto the binder mixture while agitating the mixture. The composite wasprepared as in Example 2.

The Organo-Silane Composite

The organo-silane may be present in the composite in an amount of fromabout 30% to about 80%, preferably about 50% where the organo-silane isbis(3-triethoxysilylpropyl)tetrasulfane and preferably about 60% wherethe organo-silane is UCARSIL RC-1.

The binder is present from about 20% to about 70%, most preferably about50%, where the organo-silane is bis(3-triethoxysilylpropyl)tetrasulfane,and preferably about 40%; where the organo-silane is UCARSIL RC-1.Organo silane composites may be prepared as follows.

EXAMPLE 8

A composite of dis(3-triethoxysilylpropyl)tetrasulfane was prepared asin Example 2. The binder was prepared by mixing together a 36.7% of thetotal binder weight or 9.2 grams oxidized polyethylene (VESTOWAX AO1539) and 63.3% or 15.8 grams ASTAX 140/145 paraffin having a 140-145°F. melting point. An equal weight, 25 grams ofbis(3-triethoxysilylpropyl)tetrasulfane, (DEGUSSA's Si-69) was added tothe binder mixture while agitating the mixture. The composite wasprepared as in Example 2.

EXAMPLE 9

A composite of the liquid organo-functional silane “UCARSIL RC-1” wasprepared as in Example 2. The binder was first prepared by mixingtogether a 27.5% of the total binder weight or 5.5 grams oxidizedpolyethylene, (VESTOWAX AO 1539) 47.5% or 9.5 grams ASTAX 140/145paraffin having a 140-145° F. melting point, and 25% or 5 grams ofethylene vinyl acetate copolymer resin. Then 30 grams of UCARSIL RC-1was added to the binder mixture while agitating the mixture. Thecomposite was prepared as in Example 2.

The Methacrylate Composite

The methacrylate is present in the composite in an amount from about 30%to about 80%, preferably about 60%. The binder is present from about 20%to about 70%, preferably about 30% to about 50%, most preferably about40%. A composite of trimethylolpropane trimethacrylate may be made asfollows.

EXAMPLE 10

The composite was prepared as in Example 2. The binder was prepared bymixing 36.7% of the total binder weight or 7.3 grams oxidizedpolyethylene (VESTOWAX AO 1539) and 63.3% or 12.7 grams ASTAX 140/145paraffin. Then 30 grams of trimethylolpropane trimethacrylate, (SARTOMERRESIN 350) was added to the binder mixture while agitating the mixture.The composite was prepared as in Example 2.

Organo-phosphite composite

The organo-phosphite is present in the composite in an amount from about30% to about 80%, preferably about 50%. The binder is present from about20% to about 70%, most preferably about 50%. A composite of tri(mixedmonononylphenyl and dinonylphenyl)phosphite may be made as follows.

EXAMPLE 11

A composite was prepared as in Example 2. The binder was prepared bymixing 40% of the total binder weight or 10 grams oxidized polyethylene,(VESTOWAX AO 1539) 20% or 5 grams ASTAX 140/145 paraffin, and 40% or 10grams ethylene vinyl acetate copolymer resin (ELVAX). An equal weight,25 grams, of “POLYGARD HR” a tri(mixed monononylphenyl anddinonylphenyl)phosphite, was added to the binder mixture while agitatingthe mixture. The composite was prepared as in Example 2.

The Aldehyde-Amine Reaction Product Composite

The aldehyde-amine reaction product composite is present in thecomposite in an amount from about 1 to 80% preferably 30% to about 70%,more preferably about 50%. The binder is present from about 30% to about70% preferably about 50%. A composite of the reaction product orbutyraldehyde and aniline may be prepared as follows.

EXAMPLE 12

A butyraldehyde-aniline composite was prepared as in Example 2. Thebinder was prepared by mixing together 20% of the total binder weight or5 grams of ethylene vinyl acetate copolymer resin, (ELVAX) 29.4% or 7.3grams oxidized polyethylene (VESTOWAX AO 1539) and 50.6% or 12.7 gramsASTAX 140/145 paraffin and mixed as in Example 2. A equal weight, 25grams of VANAX 808, a butyraldehyde aniline reaction product was added,and the composite was prepared as in Example 2.

While Examples 2-12 were done on a laboratory scale, the sameformulations can be adapted to a commercial scale with appropriatemodifications similar to Examples 1 and 1A.

While the invention has been described with a certain degree ofparticularity, various adaptations and modifications can be made withoutdeparting from the scope of the invention as defined in the appendedclaims.

What is claimed is:
 1. A composite useful for supplying a liquid or lowmelting point active ingredient to a vulcanizable end formulation, saidcomposite maintaining said liquid or low melting point ingredient insolid, non-powder form for facilitating handling, measuring and storingof said ingredient, said composite further having an elevated content ofsaid active ingredient while at the same time being compatible with avariety of different commercial end formulations produced on anindustrial scale, said composite comprising (a) at least thirty weightpercent, based on the total weight of the composite, of at least oneactive ingredient comprising an organic peroxide, a co-agent or amixture thereof, wherein the co-agent is a cyanurate, a polyfunctionalmethacrylate or mixtures thereof, and (b) a binder comprising a wax andoxidized polyethylene, said composite being produced by combiningcomponents (a) and (b) above together while both are in the liquid phaseto provide a homogenous mixture thereof, and thereafter causing saidhomogenous liquid mixture to solidify in the form of individual,discrete composites.
 2. The composite of claim 1 wherein said activeingredient comprises an organic peroxide.
 3. The composite of claim 2wherein said composite contains about 70 to 80 wt. % alkyl organicperoxide.
 4. The composite of claim 3 wherein said active ingredient isselected from the group consisting of dicumyl peroxide,a,a′-di(t-butylperoxy)diisopropyl benzene,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3 andn-butyl-4,4-bis(t-butylperoxy) valerate.
 5. The composite of claim 4,wherein said active ingredient is dicumyl peroxide.
 6. The composite ofclaim 3, wherein said wax is selected from the group consisting ofparaffin wax, microcrystalline wax and beeswax.
 7. The composite ofclaim 6 wherein said oxidized polyethylene has a melting point of fromabout 172° F. to about 250° F.
 8. The composite of claim 1 wherein saidoxidized polyethylene has a melting point of from about 172° F. to about250° F.
 9. The composite of claim 1 wherein said composite comprisesabout 70 to 80 wt. % dicumyl peroxide and further wherein said oxidizedpolyethylene has a melting point of from about 170° F. to about 250° F.10. The composite of claim 1 wherein said co-agent is selected from thegroup consisting of triallyl cyanurate, triallyl isocyanurate,trimethylol-propane trimethacrylate, trimethylolpropane triacylate andmixtures thereof.